Rubber vulcanization accelerator and process for preparing same



Patented Nov. 17, 1931 i h E UNITED STATES RUBBER v LoANIzATIoN ACCELERATOR annrnoonss FOR' Re ame SAME No Drawing. Original application filedau ustae, 1928, Serial No.'3o2;s9o. marina and this application filed Octobe r s, 928. SerialNo. 313,376.

This invention relates to a method for the preparation of the reaction product of a carbon disulfid derivative of a primary orsecvondary aliphatic amine with a nitro or a nitro I and halogen substituted derivative of f a phenyl' halogen me'rcaptan.v The manufacture of the preferred class of compounds will be readily understood from the following description and examples of a of'c'arryingout the invention.

The amine salts of alkyl-dithiocarbamic' acids, as are well known, are produced by the action of carbon disulfid on primary or secondary aliphatic aminesand are accelerators of the rubber-vulcanizationprocess; It has now been foundthatsuch amine salts or alkali salts of alkyl dithiocarbamic acids can be combined with a nitro substituted'phenyl halogen mercaptan to produce a stable compound having the general formula wherein R represents aliphatic hydrocarbon found to be active as accelerators of "vuIcani a commercial practice, Y 4 I The compounds of the" type comprising,

preferred mode 7 time that possess high tensile strengths and other desirable characteristics required in the subject-matter of the present invention are preferablymanufactured according 'to the following example; Thus, one ofthe preferred type of compounds, the reaction prod not of 'piperidine pentamethylene' dithiocarbamate and o-nitro-phenyl chlormerc'aptan, was prepared by dissolving substantially two molar portions of piperidine (170 parts) in" ethyl alcohol. To this alcoholic solution of piperidine, approximately one molar portion of carbon disulfid (76 parts)v was added slowly at room temperature. To the alcoholic solution of piperidinev penta-methylene dithioca'rbamate thus prepared, substantially one molar portion (l90 parts) of o-nitrophenyl chlormercaptan was added with agi-' tation and while maintaining a temperature of approximately 20 to C. After the materials had been combined in the manner described, agitation was continued for about three hours at a temperatureof substantially 20 to 509C. .Iheyellow'solid formed, com- PATENT ounce i wIivrInnn soon, or NITR O, wnsr VIRGINIA, asmdm Tia-n humans snR vIcEif. LABORATORIES (20., or AK ON,om 'acom onnrzon or, onIo a 1 prising the desired material, was filtered off, i

washed with'alcohol and dried at'a tempera-J ture of about 50 This material, which is soluble in alcohol, benzene and I chloroform,

possesses a melting point of substantially 1233 to,124=,3, G. and is most probably formed cording to the following equation:

lzationwh'en employed in a rubber inixand As another methodofpreparingtheabove" 5o produce rubber products in a short' period of compound, in pla'oe of the piperidine'saltof pentamethylene dithiocarbamic acid, the so- 7 diumsalt of pentamethylene dithiocarbamic acid was reacted with o-nitro-phenyl chlor- .mercaptan according to the following procedure. v

t t V Approximately one molar portion of sodium hydroxide parts) was dissolved in about 1200 partsof ethyl alcohol. Approxi mately one molar portion of piperidine.l(85 10 parts) was added theretoand then substantially one molar portion of carbon disulfid (76 parts) was addedat room temperature.

and driedwat about,50. G. If prepared according-.to'this method, the formation of the desired material most-probably takes place according to the following equation:

pounds, for-example the reaction product of o-nitro-phenyl chlormercaptan and diethyl-C- amine, diethyl dithiocarbamate, was prepared in an analogous manner tothe'reaction product of o-nitro-phe'nyl' chlormercaptan and piperidine pentamethylene dithiocarba mate' hereinbefore mentioned. The material so obtainedwas aiyellow solid, soluble in. alcohol and chloroform, and possesses a melting'point of substantially 90.1to 922 C.

Other examples of the preferred class of" compounds, for example the reaction prod} not of dinitro-phenyl chlormercaptan and piperidine pentamethylene dithiocarbamate and the reaction product of chlor-nitrophenyl chlo mercaptan and normal dibutylamine dibutylfdithiocarbamate. were prepared in a manner similar to that used in the prepara- 693 tion of'the reaction product of o-nitro-phenyl chlormercaptan and piperidine pentamethylene dithiocarbamate. '--.All ofthe materials,

the preparation of which is described in this specification, on testing were found :to t be 5' Valuable vulcanization accelerators.

. phenyl halogen mercaptan.

Another of the 'preferred class ofcom- Having thus described these examples of the invention, I do not wish to be understood as being limited to the exact proportions, ingredients, temperatures and steps set forth,

for various changes may be made without departing from the essentialfeatures of my invention. The invention is limited solely by the claims attached hereto as a part of this specification wherein it is intended'to claim the invention .as'broadly as possible.

This case is a; division of application Serial No. 302,890,--filed-August 29,1928, by the present applicant. What isclaimedis:

l. A process ofpreparing a rubber vulcanizationaccelerator which comprises reacting a di-thio-carbamate with a nitro substituted 2. A process of preparing a rubber vulcanization accelerator which comprises reacting a di-thio-carbamate with anitro substitutedphenyl chlormercaptana 3. A process of preparing a rubbervulcam 1zat1on accelerator, WlllCh compr ses reacting,

a di-thio-carbamate with. o-nitro-phenyl chlorinercaptan. I V i A. A process of preparinga rubber vulcane ization accelerator, which comprises reacting,

a salt: of a substituted dithiocarbamic acid p with o-nitro-phenyl chlormercaptan. i

t 5. A process of preparing a=rubber vulcanization accelerator which comprises reacting an amlne 'salt of a substituted d1th1ocarbam1c acid with o-nitro-phenylchlorinercaptan.

6. A process of preparing 'a rubber vulcanization acceleratorwhich comprises reacting 7 an amine salt of an alkyl substituted dithiocarbamic acid with o-nit'ro-phenyl chlormercaptan.

7. A process of preparing a rubber vulcanization accelerator which comprises reacting piperidine pentamethylene dithiocarbamate with o-nitro-phenyl chlormercaptan.

8. A process of preparing a rubber vulcanization accelerator which comprises'reacting substantially equi-molar portions of piperidine pentamethylene dithiocarbamate and og-nitro-phenyl chlorme'rcapt'an.

91' A process of preparing a rubbervulc'anization accelerator which comprises reacting adi-thio-carbamate with a nitro substituted arylhalogen mercaptan.

l0'.'-A process of preparing a rubbervuloanizatlon accelerator which comprises reacting substantially equi-molar portions of piperidine pentamethylene dithiocarbamate and o-nitro-phenyl chlormercaptan at a temperature below 50 C.

, 1 1 'The product'formed by reacting a dithio-'carba-mate with a nitro substituted 'phenyl halogen mercaptan.

12. The product formed by reacting a di- 7 hiQ- e b m e W t-i ez ny hler- 13. The product formed by reacting substantially equi-molar portions of piperidine pentamethylene dithiocarbamate and o-nitrophenyl chlormeroapta-n.

14. As a new product the material formed by reacting piperidine pentamethylene dithiocarbamate and o-nitro-phenyl chlormercaptan, which is a solid melting at substantially between 123 to 125 C5 and is soluble in alcohol, benzene and chloroform.

15'. The product formed by reacting a dithio-carbamate with a nitro substituted phenyl chlormercaptan. r

In testimony whereof I hereunto afiix my signature.

WINFIELD SCOTT.

DISCLAIMER 1,832,328.Wi12field Scott, Nitro, W. Va. RUBBER VULCANIZATION AccELERA'roR AND PROCESS FOR PREPARING SAME. Patent dated November 17, 1931. Disclaimer filed September 17, 1935, by the assignee, The Rubber Service Laboratories C0. Hereby disclaim that part of the claim in said specification which is in the following words, to wit:

1. A process of preparing a rubber vulcanization accelerator which comprises reacting a di-thio-carbamate with a nitro substituted phenyl halogen mercaptan.

9. A process of preparing a rubber vulcanization accelerator which comprises reacting a di-thio-carbamate with a nitro substituted aryl halogen mercaptan.

11. The product formed by reacting a di-thio-carbamate with a nitro substituted phenyl halogen mercaptan.

[Ojficz'al Gazette October 15, 1.935.] 

